Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
  • C07C35/22—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system
  • C07C35/37—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with a hydroxy group on a condensed system having three rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/56—Ring systems containing bridged rings
  • C07C2603/58—Ring systems containing bridged rings containing three rings
  • C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
  • C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings

Definitions

• the present invention relates to the compound 4-exohydroxy-endo-tricyclo[ 5.2.2.0 2 ,6 ] undec-8-ene, a novel tricyclic unsaturated alcohol having the formula (I): ##STR3## and a process for preparing same. More particularly, the invention relates to a process for preparing the formula (I) compound by subjecting endo-tricyclo[ 5.2.2.0 2 ,6 ] undeca-3,8-diene having the formula (II): ##STR4## to oxymercuration and reduction with sodium borohydride.
• the compound of formula (I) is a novel substance. Because it has a polycyclic aliphatic structure like those of natural sesquiterpene alcohols and synthetic tricyclic aliphatic alcohols such as adamantyl alcohol, this compound will have substantially the same physiological activities as those known compounds, such as an anti-viral activity, an antifungal activity and a plant-growth stimulating activity and it will also be useful as an active odor-imparting ingredient of perfume compositions. Still further, as a great number of natural and synthetic aliphatic polycyclic compounds are incorporated as modifying groups into various pharmaceutical compounds and physiologically active compounds to improve the effects of those compounds, the compound of the present invention can be utilized similarly to those known compounds.
• Aliphatic polycyclic compounds for example, adamantane derivatives are distinguished from linear aliphatic compounds and from aromatic compounds in the features that they can be used as bases and as additives of lubricating oil compositions, fiber oiling compositions and components thereof, rust preventing compositions, extreme pressure additives and synthetic macromolecular monomers.
• the compound of the present invention will also have these valuable properties. Accordingly, the compound of the present invention is valuable, per se, and as an intermediate and it can be used in various fields.
• 4-exo-hydroxy-endo-tricyclo[ 5.2.2.0 2 ,6 ] undec-8-ene having the formula (I) is synthesized by reacting endo-tricyclo[ 5.2.2.0 2 ,6 ] undeca-3,8-diene having the formula (II) with mercuric acetate to effect a so-called oxymercuration and then reducing the resulting organic mercury intermediate with sodium borohydride.
• the 13 C NMR spectrum of the compound (I) consists of 6 absorptions, and the relative intensity of one absorption is 1 and the relative intensity of each of the remaining 5 peaks is 2. From this fact, it is apparently proved that the hydroxyl group is substituted at the 4-position. In other words, if the hydroxyl group is substituted at any of the 3-, 8- and 9-positions, the molecule will be asymmetric all the 13 C NMR spectrum will have to show 11 absorptions.
• the 13 C signal having a relative intensity of 1 (attributed to the carbon atom at the 4-position) appears in a region of a lower magnetic field (73.6 ppm) than the other signals, and the influence of the substitution by the hydroxyl group is readily understood.
• an unsaturated alcohol of the following formula (IV), which is different from the compound (I), is formed by oxidizing the compound (I) and then reducing the oxidized product with lithium aluminum hydride, it is apparent that the hydroxyl group at the 4-position is of the exo-arrangement.
• the reaction formula given below in the reduction of a polycyclic ketone with lithium aluminum hydride, it is established that the reagent approaches the exo-side of a reduced steric hindrance (the so-called steric approach control) and the resulting alcohol comes to have an endo-arrangement [see, for example G. R. Wenzinger and J. A. Ors, J. Org.
• the unsaturated alcohol (IV) necessarily takes the endo-arrangement as shown by formula (IV), and hence, the compound (I) having an arrangement different from that of the alcohol (IV) is an exo-alcohol of formula (I).
• the conventional method of oxymercuration and reduction with sodium borohydride [H. C. Brown et al, J. Org. Chem. 35, 1844 (1970)] can be directly applied to the starting substance (II). Since the selectivity of formulation of the formula (I) compound in this reaction is very high, as pointed out hereinabove, the formula (I) compound can be isolated from the reaction mixture very easily. That is, the formula (I) compound, of a high purity, can be obtained in a good yield by extracting the reaction mixture with a suitable organic solvent, for example, diethyl ether and recrystallizing the extract.
• a suitable organic solvent for example, diethyl ether and recrystallizing the extract.
• the diolefin (II) that is used as the starting substance in the process of the present invention can be prepared, for example, by Diels-Alder reaction between 1,3-cyclohexadiene and cyclopentadiene [Italian Patent No. 730 703 Dec. 1, 1966), Takaishi, Inamoto, Aigami, Tsuchihashi and Ikeda, Synth. Commun., 4, 225 (1974) and Takaishi, Inamoto and Aigami, J. Org. Chem., 40, 276 (1975)].
• the low-boiling-point solvent was distilled off under reduced pressure, and the residual crude alcohol was recrystallized from n-hexane to give 54.2 g (0.33 mole) of needle-like crystals of 4-exo-hydroxy-endo-tricyclo[ 5.2.2.0 2 ,6 ]undec-8-ene (I), melting at 98° to 99° C. The yield was 82%.
• Chick embryo fibroblasts were cultured for 2 to 3 days in a test tube according to the monolayer culture method and were inoculated with Newcastle disease virus of about 128 HAU (hamagglutination units).
• a culture medium of the stepwise dilution system containing a compound as listed below was added to the upper layer and the culturing was continued for 48 hours at 37° C.
• the anti-viral effect was evaluated based on the hemagglutination reaction. The results obtained are shown below.
• the formula (I) compound exhibits a more intense anti-viral activity than that of adamantylamine hydrochloride, a known useful anti-viral substance.
• the formula (I) compound can be used in the same way as adamantylamine hydrochloride, adjusting the dosage amounts as needed to reflect the more intense anti-viral activity of the formula (I) compound.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Publications (1)

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Family Applications (1)

Country Status (5)

Cited By (3)

Citations (4)

• 1975
  • 1975-05-26 JP JP50062816A patent/JPS51138664A/ja active Granted
• 1976
  • 1976-05-07 US US05/684,395 patent/US4036892A/en not_active Expired - Lifetime
  • 1976-05-08 DE DE19762620379 patent/DE2620379A1/de not_active Withdrawn
  • 1976-05-10 GB GB19158/76A patent/GB1490047A/en not_active Expired
  • 1976-05-21 CH CH646076A patent/CH596123A5/xx not_active IP Right Cessation

Patent Citations (4)

Non-Patent Citations (3)

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